DE959402C - Light stabilizers - Google Patents

Light stabilizers

Info

Publication number
DE959402C
DE959402C DEB24711A DEB0024711A DE959402C DE 959402 C DE959402 C DE 959402C DE B24711 A DEB24711 A DE B24711A DE B0024711 A DEB0024711 A DE B0024711A DE 959402 C DE959402 C DE 959402C
Authority
DE
Germany
Prior art keywords
thiodiazole
ethanol
oxdiazole
methanol
light stabilizers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
DEB24711A
Other languages
German (de)
Inventor
Dr Karl-Erich Kling
Dr Hans Krzikalla
Dr Heinz Pohlemann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to DEB24711A priority Critical patent/DE959402C/en
Application granted granted Critical
Publication of DE959402C publication Critical patent/DE959402C/en
Expired legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/496—Triazoles or their condensed derivatives, e.g. benzotriazoles

Description

Lichtschutzmittel Es ist bekannt, Stoffe, die bestimmte Bereiche der UV-Strahlung absorbieren, als Licht- und Sonnenschutzmittel zu verwenden, um z. B. die Haut vor der erythemerzeugenden UV-B-Strahlung (etwa 280 bis 320 m,lz) zu schützen und dadurch Sonnenbrand zu verhindern. Solche Stoffe sind z. B. die aus dem deutschen Patent 873 733 bekannten heterocyclisch substituierten Sulfonamide. Sie haben jedoch den Nachteil, daß ihre lichtschützende Wirkung nur gering ist und daß sie als Sulfonamide der Rezeptpflicht unterliegen, da ihre Anwendung nicht ungefährlich ist. Beispielsweise kann der menschliche Organismus allein durch das Bestreichen der Haut mit diesen Stoffen so an sie gewöhnt werden, daß die Verabreichung von Sulfonamiden bei einer späteren Infektion wirkungslos ist.Light stabilizers It is known substances that affect certain areas of the Absorb UV radiation, use as a light and sun protection agent, e.g. B. the skin from the erythema-producing UV-B radiation (about 280 to 320 m, lz) protect and thereby prevent sunburn. Such substances are z. B. the the German patent 873 733 known heterocyclically substituted sulfonamides. However, they have the disadvantage that their light-protecting effect is only slight and that, as sulfonamides, they are subject to prescription requirements, as their use is not without danger is. For example, the human organism can simply brush it the skin with these substances become so accustomed to them that the administration of Sulfonamides is ineffective in a later infection.

Es wurde nun gefunden, daß überraschenderweise sulfonamidgruppenfreie I, 3, 4-Oxdiazole, I, 3, 4-Thiodiazole oder I, 2, 4-Triazole wesentlich besser als Lichtschutzsubstanzen geeignet sind. It has now been found that, surprisingly, sulfonamide groups-free I, 3, 4-oxdiazoles, I, 3, 4-thiodiazoles or I, 2, 4-triazoles are much better than Light protection substances are suitable.

Beispielsweise eignen sich ausgezeichnet die an einem oder beiden Kohlenstoffatomen des Moleküls substituierten Derivate, z. B. die Alkyl-, Aralkyl-, Aryl- oder Cycloalkylderivate, wobei in diesen Substituenten weitere Gruppen, wie Hydroxyl-, Amino-, Methyl-, Alkoxy-, organische Säureamid-, Nitro-, Carboxyl- oder sulfonsaure Gruppen substituiert sein können. Weiterhin kann das Wasserstoffatom an mindestens einem der beiden Kohlenstoffatome des Oxdiazols, des Thiodiazols oder Triazols durch einen heterocyclischen Rest, z. B. Furyl- oder Nicotyl-, oder einen anorganischen Substituenten, beispielsweise durch eine Sulfonsäure- oder Merkaptogruppe, substituiert sein. Diese Substituenten können dabei, soweit sie mit basischen Stoffen, wie organischen Basen, Alkalien einschließlich des Ammoniums sowie der Erdalkalien, Salze bilden, als solche vorliegen oder in Ester oder Äther übergeführt sein. Je nach Wahl der Substituenten und dem Verwendungszweck kann man Ö1-, Wasser- oder Alkohollöslichkeit erzielen sowie das Absorptionsmaximum, das vorzugsweise bei 305 mµ, aber nicht wesentlich unterhalb von 290 mjt bzw. oberhalb von 320 mµ liegen soll, verschieben. Die gleiche Wirkung läßt sich auch durch Mischung mehrerer dieser Verbindungen erreichen. For example, those on one or both are excellent Carbon atoms of the molecule substituted derivatives, e.g. B. the alkyl, aralkyl, Aryl or cycloalkyl derivatives, with further groups in these substituents, such as Hydroxyl, amino, methyl, alkoxy, organic acid amide, nitro, carboxyl or sulfonic acid groups can be substituted. Furthermore, the hydrogen atom at at least one of the two carbon atoms of oxdiazole, thiodiazole or Triazole by a heterocyclic radical, e.g. B. furyl or nicotyl, or one inorganic substituents, for example by a sulfonic acid or mercapto group, be substituted. These substituents can, insofar as they are associated with basic substances, such as organic bases, alkalis including ammonium and alkaline earths, Form salts, exist as such or be converted into esters or ethers. Ever according to the choice of substituents and the intended use can be oil, water or Achieve alcohol solubility and the absorption maximum, which is preferably at 305 mµ, but not significantly below 290 mJt or above 320 mµ should move. The same effect can also be achieved by mixing several of these Achieve connections.

Bei einem Zusatz von I bis 10% zu den üblichen Lichtschutzgrundlagen, wie Vaselin und anderen Salbengrundstoffen, Ölen, Polyglykolen, Carbinolen und auch Wasser, weisen die neuen Lichtschutzmittel neben guter Verträglichkeit bei einer Schichtdicke von 0,01 mm eine Lichtdurchlässigkeit der Wellenlänge von 3I3 m,u von maximal 5% auf. With an addition of 1 to 10% to the usual light protection bases, like vaseline and other ointment base materials, oils, polyglycols, and carbinols too The new light stabilizers have water, in addition to being well tolerated by a Layer thickness of 0.01 mm a light transmission of the wavelength of 3I3 m, u of a maximum of 5%.

In gleicher Konzentration in Flächengebilde, z. B. transparenten Folien, eingearbeitet, erteilen sie diesen ebenfalls ausgezeichnete lichtschützende Eigenschaften. In the same concentration in flat structures, e.g. B. transparent Films, incorporated, give them excellent light-protecting properties Properties.

Viele Vertreter der hier vorgeschlagenen Gruppe von Lichtschutzmitteln sind in der Literatur noch nicht beschrieben. Man erhält sie nach den in der organischen Chemie üblichen Verfahren, z. B. aus den symmetrisch oder unsymmetrisch substituierten Diacylhydrazinen durch Wasserabspaltung bzw. durch Umsatz mit Phosphorpentasulfid oder Ammoniak unter Druck. Many representatives of the group of light stabilizers proposed here are not yet described in the literature. They are obtained according to the organic Chemistry usual methods, e.g. B. from the symmetrically or asymmetrically substituted Diacylhydrazines through elimination of water or through reaction with phosphorus pentasulfide or ammonia under pressure.

Im folgenden werden für einige der Lichtschutzmittel, die in einer Schichtdicke von I cm in einem Lösungsmittel bei angegebener Konzentration mit einem Beckmann-Spektralphotometer bei Raumtemperatur gemessenen Absorptionsmaxima sowie die zugehörigen prozentualen Lichtdurchlässigkeiten aufgeführt. Lichtdurch- Konzentration Lösungs- # max lässigkeit Substanz in Volum- mittel in mµ bei # max I. 2-Methyl-5-p-aminophenyl-I, 3, 4-oxdiazol... Methanol 0,OOI 302 4,00 2. 2-Äthyl-5-p-aminophenyl-1, 3, 4-oxdiazol ... Äthanol 0,OOI 302 6,oo 3. 2-Pentadecyl-5-p-aminophenyl-1, 3, 4-oxdiazol Methanol 0,OOI 304 23,00 4. 2-Heptadecyl-5-p-aminophenyl-1,3,4-oxidazol Äthanol 0,001 303 27,00 5. 2-Heptadecen(8)-5-p-aminophenyl-1, 3, 4-ox- diazol s Athanol O,OOI 305 24,50 6. 2-Pentadecyl-5-p-nitrophenyl-I, 3, 4-oxdiazol Methanol O,OOI 288 37,00 7. 2, 5-Di-[sulfophenyl]-1, 3, 4-oxdiazol........ Wasser 0,001 280 7,00 8. 2, 5-Diphenyl-1, 3, 4-oxdiazol................ Methanol 0,001 280 25,00 9. 2, 5-Di-p-Tolyl-1, 3, 4-oxdiazol ............. Methanol 0,001 287 6,80 10. 2, 5-Distyryl-1, 3, 4-oxdiazol .............. Methanol 0,001 328 9,50 11. 2, 5-Di-[2-Oxy-5-methyl-phenyl]-1, 3, 4-ox- diazol ................................ Dimethyl- 0,001 332 21,00 formamid 12. 2-(p-Natrium-Succinyl-aminophenyl)- 5-Methyl-1, 3, 4-oxdiazol................ Wasser 0,002 280 2,00 13. 2-(p-Maleinylaminophenyl)-5-Methyl- 1, 3, 4-oxdiazol ........................ Wasser mit 0,002 296 3,00 einigen Tropfen NH3 14. 2, 5-Diisonikotyl-1, 3, 4-thiodiazol.......... Äthanol 0,001 289 10,50 15. 2, 5-Dinikotyl-1, 3, 4-thiodiazol ............. Methanol 0,001 304 10,00 16. 2, 5-Diphenyl-1, 3, 4-thiodiazol .............. Methanol 0,001 298 11,00 17. 2-Phenyl-5-nikotyl-1, 3, 4-thiodiazol.......... Methanol 0,001 300 11,00 18. 2, 5-Di(-p-carboxyphenyl)-I, 3, 4-thiodiazol Methanol 0,001 299 14,00 19. 2,5-Di(methyl-merkapto)-1, 3, 4-thiodiazol .. Äthanol 0,005 290 0,00 20. 2,5-Di-(äthyl-merkapto)-1, 3, 4-thiodiazol ... Äthanol 0,005 290 o,50 Lichtdurch- Konzentration Lösungs- # max lässigkeit Substanz in Volum- mittel in mµ bei # max prozent in % 21. 2, 5-Di-(isopropyl-merkapto)-I, 3, 4-thiodiazol Äthanol 0,005 293 0,75 22. 2, 5-Di-(isobutyl-merkapto)-I, 3, 4-thiodiazol Äthanol 0,005 292 0,80 23. 2, 5-Di-(butyl-merkapto)-I, 3, 4-thiodiazol... Äthanol 0,005 290 I,75 24. 2, 5-Di-(carboxy-methylmerkapto)-I,3, 4-thio- diazol . Äthanol 0,005 288 I,75 25. [2-Methyl-5-ß-oxyäthyl]-dimerkapto- 1, 3, 4-thiodiazol...................... Äthanol 0,005 291 1,21 26. [2-Methyl-5-äthyl]-dimerkapto-I, 3, 4-thio- diazol ................................. Athanol 0,003 290 2,50 27. 2, 5-Bis-(natriurnmerkapto)-I, 3, 4-thiodiazol Wasser 0,003 3I7 4,00 28. 2, 2'-Dithio-bis-(5-methylmerkapto)- 1, 3, 4-thiodiazol ..................... Äthanol 0,003 305 0,50 29. 2-Merkapto-5-methylmerkapto-I, 3, 4-thio- diazol .............................. Äthanol 0,005 319 0,00 30. Natriumsalz von 29 ...................... Wasser 0,003 310 3,50 31. Triäthanolaminsalz von 29 ............... Wasser 0,005 309 1,50 32. 2,5-Di-[benzylmerkapto]-1, 3, 4-thiodiazol .. Äthanol 0,001 295 44,00 33. 2-Carboxymethylmerkapto-5-merkapto- I, 3, 4-thiodiazol ............... Wasser mit 0,003 310 5,00 einigen Tropfen NH3 34. 2-Merkapto-5-benzylmerkapto-1, 3, 4-thio- diazol ............................... - 0,005 309 1,00 35. 2-Merkapto-5-ß-oxyäthylmerkapto- 1, 3, 4-thiodiazol.................... - 0,005 310 1,00 36. 2-Merkapto-5-äthylmerkapto-I, 3, 4-thiodiazol - 0,005 310 0,00 37. 2-Merkapto-5-butylmerkapto-1, 3, 4-thiodiazol Äthanol 0,005 32I 0,00 In the following, the absorption maxima measured with a Beckmann spectrophotometer at room temperature and the associated percentage light transmittances are listed for some of the light stabilizers in a layer thickness of 1 cm in a solvent at the specified concentration. Light transmission concentration Solution # max permeability Substance in volume mean in mµ at # max I. 2-methyl-5-p-aminophenyl-1,3,4-oxdiazole ... methanol 0, OOI 302 4.00 2. 2-Ethyl-5-p-aminophenyl-1, 3, 4-oxdiazole ... Ethanol 0, OOI 302 6, oo 3. 2-Pentadecyl-5-p-aminophenyl-1,3,4-oxdiazole methanol 0, OOI 304 23.00 4. 2-heptadecyl-5-p-aminophenyl-1,3,4-oxidazole ethanol 0.001 303 27.00 5. 2-heptadecene (8) -5-p-aminophenyl-1, 3, 4-ox- diazol s ethanol O, OOI 305 24.50 6. 2-Pentadecyl-5-p-nitrophenyl-1,3,4-oxdiazole methanol O, OOI 288 37.00 7. 2, 5-di- [sulfophenyl] -1, 3, 4-oxdiazole ........ water 0.001 280 7.00 8. 2, 5-Diphenyl-1, 3, 4-oxdiazole ................ Methanol 0.001 280 25.00 9.2, 5-di-p-tolyl-1, 3, 4-oxdiazole ............. methanol 0.001 287 6.80 10. 2, 5-distyryl-1, 3, 4-oxdiazole .............. methanol 0.001 328 9.50 11. 2, 5-di- [2-oxy-5-methyl-phenyl] -1, 3, 4-ox- diazole ................................ dimethyl- 0.001 332 21.00 formamide 12. 2- (p-Sodium-succinyl-aminophenyl) - 5-methyl-1,3,4-oxdiazole ................ water 0.002 280 2.00 13. 2- (p-Maleinylaminophenyl) -5-methyl- 1, 3, 4-oxdiazole ........................ water with 0.002 296 3.00 some Drop of NH3 14. 2, 5-diisonicotyl-1, 3, 4-thiodiazole .......... ethanol 0.001 289 10.50 15. 2, 5-Dinicotyl-1, 3, 4-thiodiazole ............. Methanol 0.001 304 10.00 16. 2, 5-Diphenyl-1, 3, 4-thiodiazole .............. methanol 0.001 298 11.00 17. 2-Phenyl-5-nicotyl-1, 3, 4-thiodiazole .......... methanol 0.001 300 11.00 18. 2, 5-di (-p-carboxyphenyl) -I, 3, 4-thiodiazole methanol 0.001 299 14.00 19. 2,5-Di (methyl-merkapto) -1, 3, 4-thiodiazole .. Ethanol 0.005 290 0.00 20. 2,5-Di- (ethyl-merkapto) -1, 3, 4-thiodiazole ... ethanol 0.005 290 o, 50 Light transmission concentration Solution # max permeability Substance in volume mean in mµ at # max percent in % 21. 2,5-Di- (isopropyl-merkapto) -I, 3, 4-thiodiazole ethanol 0.005 293 0.75 22. 2,5-Di- (isobutyl-merkapto) -I, 3, 4-thiodiazole ethanol 0.005 292 0.80 23. 2,5-Di- (butyl-merkapto) -I, 3, 4-thiodiazole ... ethanol 0.005 290 I, 75 24. 2, 5-Di- (carboxy-methylmercapto) -I, 3, 4-thio- diazole. Ethanol 0.005 288 1.75 25. [2-Methyl-5-ß-oxyethyl] -dimerkapto- 1, 3, 4-thiodiazole ...................... ethanol 0.005 291 1.21 26. [2-Methyl-5-ethyl] -dimerkapto-I, 3, 4-thio- diazole ................................. ethanol 0.003 290 2.50 27. 2, 5-bis (sodium mercapto) -I, 3, 4-thiodiazole water 0.003 3I7 4.00 28. 2, 2'-dithio-bis- (5-methylmercapto) - 1, 3, 4-thiodiazole ..................... ethanol 0.003 305 0.50 29. 2-Merkapto-5-methylmercapto-I, 3, 4-thio- diazole .............................. ethanol 0.005 319 0.00 30. Sodium salt of 29 ...................... water 0.003 310 3.50 31. Triethanolamine salt of 29 ............... water 0.005 309 1.50 32. 2,5-di- [benzylmercapto] -1, 3, 4-thiodiazole .. ethanol 0.001 295 44.00 33. 2-carboxymethyl mercapto-5-mercapto I, 3, 4-thiodiazole ............... water with 0.003 310 5.00 some Drop of NH3 34.2-Mercapto-5-benzylmercapto-1, 3, 4-thio- diazole ............................... - 0.005 309 1.00 35.2-Mercapto-5-ß-oxyäthylmercapto- 1, 3, 4-thiodiazole .................... - 0.005 310 1.00 36. 2-Merkapto-5-ethylmercapto-1,3,4-thiodiazole - 0.005 310 0.00 37. 2-Merkapto-5-butylmercapto-1, 3, 4-thiodiazole ethanol 0.005 32I 0.00

Claims (1)

PATENTANSPRUCH: Die Verwendung von sulfonamidgnippenfreien I, 3, 4-Oxdiazolen, I, 3, 4-Thiodiazolen oder 1, 2, 4-Triazolen als Lichtschutzmittel.PATENT CLAIM: The use of sulfonamide group-free I, 3, 4-oxdiazoles, I, 3, 4-thiodiazoles or 1, 2, 4-triazoles as light stabilizers. In Betracht gezogene Druckschriften: Deutsche Patentschrift Nr. 873 733. Publications considered: German Patent No. 873 733
DEB24711A 1953-03-13 1953-03-13 Light stabilizers Expired DE959402C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3173842A (en) * 1963-09-03 1965-03-16 Olin Mathieson Process for waving human hair with 2, 5-dimercaptothiodiazoline
US20140301975A1 (en) * 2006-05-09 2014-10-09 Phoenicia Biosciences, Inc. Methods for Treating Blood Disorders

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE873733C (en) * 1942-07-24 1953-04-16 Hydrierwerke A G Deutsche Light stabilizers

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE873733C (en) * 1942-07-24 1953-04-16 Hydrierwerke A G Deutsche Light stabilizers

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3173842A (en) * 1963-09-03 1965-03-16 Olin Mathieson Process for waving human hair with 2, 5-dimercaptothiodiazoline
US20140301975A1 (en) * 2006-05-09 2014-10-09 Phoenicia Biosciences, Inc. Methods for Treating Blood Disorders
US9095565B2 (en) * 2006-05-09 2015-08-04 Phoenicia Biosciences, Inc. Methods for treating blood disorders

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